Soldering alloy, soldering paste, preform solder, soldering ball, wire solder, resin flux cored solder, solder joint, electronic circuit board, and multi-layer electronic circuit board

ABSTRACT

A soldering alloy includes an alloy composition consisting of 13-22 mass % of In, 0.5-2.8 mass % of Ag, 0.5-5.0 mass % of Bi, 0.002-0.05 mass % of Ni, and a balance Sn. A soldering alloy, a soldering paste, a preform solder, a soldering ball, a wire solder, a resin flux cored solder and a solder joint, each of which is composed of the soldering alloy. An electronic circuit board and a multi-layer electronic circuit board joined by using the solder joint.

FIELD

The present invention relates to a soldering alloy of which a main component is Sn, a use of the soldering alloy, and an electronic circuit board in which the soldering alloy is used.

BACKGROUND

In recent years, lead-free soldering alloy that does not contain lead has been used in consideration of environment. Examples of the lead-free soldering alloy include SAC305 (Sn-3.0Ag-0.5Cu). A melting point of SAC305 is about 220° C. During a soldering with SAC305, a peak temperature of a reflow oven is generally set to an intermediate temperature range of about 250° C.

On the other hand, in order to suppress thermal loads on a miniaturized electronic part, the soldering performed in a low temperature range has also been required. In the soldering in the low temperature range, the lead-free soldering alloy having a low melting point is used. Such the soldering alloy include Sn-58Bi and Sn-521n. The melting point of Sn-58Bi is about 140° C. That of Sn-52In is about 120° C. During the soldering performed in the low temperature range, the peak temperature of the reflow oven is generally set to 150-160° C.

Incidentally, in a step-soldering where the soldering is performed in multiple stages, the soldering is expected to be performed at an intermediate temperature range between the above-mentioned intermediate temperature and low temperature. Examples of prior arts related to the lead-free soldering alloy having the melting point in such the intermediate temperature range include Patent Document 1. Patent Document 1 discloses a lead-free soldering alloy consisting of three elements of Sn, Ag and In. This conventional soldering alloy has a solidus temperature of 167-212° C. and a liquidus temperature of 179-213° C.

Examples of the prior arts related to the present application include Patent Document 2. Patent Document 2 discloses a lead-free soldering alloy consisting of Sn, In, Ag and Cu. Patent Document 2 discloses several examples in which these essential elements are different in content. Each of the solidus temperature of these examples is about 120° C.

Another example of the prior art related to the present application includes Patent Document 3. Patent Document 3 discloses a lead-free soldering alloy consisting of 0.5 to 5 mass % of Ag, 0.5 to 20 mass % of In, 0.1 to 3 mass % of Bi, 3 mass % or less of an additive element, and balance Sn. The additive element is at least one element selected from Sb, Zn, Ni, Ga, Ge and Cu. Patent Document 3 discloses examples of the alloys that contain 0.5 and 1.5 weight % of Ni as the additive element.

CITATION LIST Patent Literature

-   [PTL 1] JPH6-15476A -   [PTL 2] JP2013-198937A -   [PTL 3] JP2004-188453A

SUMMARY Technical Problem

The lead-free soldering alloy that simply has the low melting point is not suitable for a step-soldering including the soldering performed in the above-mentioned intermediate temperature range. That is, the property that melts at a temperature below the melting point of the low-temperature soldering alloy represented by Sn-58Bi leads to a possibility of being re-melted in the soldering step of the low-temperature soldering alloy. Therefore, the soldering alloy of Patent Document 2 having the solidus temperature lower than the melting point of the low-temperature soldering alloy cannot be subjected to the soldering step that is different from the soldering step of the said low-temperature soldering alloy.

In addition, the soldering alloy of Patent Document 3 has not been developed focusing on its melting point. Therefore, it is not known whether or not the soldering alloy of Patent Document 3 is suitable for the soldering performed in the above-mentioned intermediate temperature range.

It is important that the soldering alloy suitable for such the step-soldering not only meets the requirement on the melting point but also has excellent in a mechanical reliability. Therefore, there is room to develop the soldering alloy focusing on these viewpoints.

One object of the present invention is to provide a soldering alloy which is suitable for the step-soldering including the soldering performed in the intermediate to low temperature range and which has excellent in the mechanical reliability. Another object of the present invention is to provide a soldering paste, a preform solder, a soldering ball, a wire solder, a resin flux cored solder and a solder joint including such the soldering alloy. It is yet another object of the present invention to provide an electronic circuit board and a multi-layer electronic circuit board to which such the soldering alloy is applied.

Solution to Problem

Inventors of the present invention started with a Sn—In alloy consisting of two elements, Sn and In. When a content of In exceeds a certain amount, this alloy forms an intermetallic compound phase called a γ phase composed of In and Sn. However, since this γ phase is brittle, there is a risk of lowering a ductility of the soldering alloy. Therefore, the content of In was set around 20 weight % such that a desired mechanical property could be achieved without decreasing the ductility.

After determining the content of In, an additive element to a soldering alloy having an appropriate melting point that is subjected to the soldering with the intermediate to low temperature range was investigated. Consequently, it was found that not only the melting point is adjusted to the appropriate range but also the mechanical property is improved by adding an appropriate amount of Ag, Bi and Ni to the Sn—In based alloy. From the above investigation, it was found that a soldering alloy obtained by adding an appropriate amount of five elements of Sn, In, Ag, Bi and Ni is an optimum soldering alloy for solving the above-described problems.

A first invention is a soldering alloy having the following features.

The soldering alloy includes an alloy composition consisting of 13-22 mass % of In, 0.5-2.8 mass % of Ag, 0.5-5.0 mass % of Bi, 0.002-0.05% of Ni, and a balance of Sn.

A second invention has the following features in the first invention.

The alloy composition further contains, at least one selected from P, Ge and Ga in total of 0.09 mass % or less.

A third invention has the following features in the first or second invention.

The alloy composition further contains 0.005-0.1 mass % of Sb.

A fourth invention has the following features in any one of the first to third inventions.

The content of In is 15-20%.

A fifth invention has the following features in the fourth invention.

An upper limit of the content of In is 17%.

A sixth invention has the following features in any one of the first to fifth inventions.

The content of Ag is 1.0-2.5%.

A seventh invention has the following features in any one of the first to sixth inventions.

The content of Bi is 1.0-2.5%.

An eighth invention has the following features in any one of the first to seventh inventions.

The content of Ni is 0.003-0.04%.

A ninth invention has the following features in any one of the first to eighth inventions.

The content of In, Ag, Bi, and Ni satisfies the following relationship (1).

0.9≤(In×Ni)×(Ag+Bi)≤3.4  (1)

In the relationship (1), In, Ni, Ag, and Bi represent each content of the respective elements.

A tenth invention further has the following features in any one of the first to ninth inventions.

A solidus temperature of the soldering alloy is 160° C. or more.

A liquidus temperature of the soldering alloy is 210° C. or less.

An eleventh invention further has the following features in the tenth invention.

The solidus temperature is 165° C. or higher.

The liquidus temperature is 200° C. or less.

A twelfth invention is a soldering paste.

The soldering paste consists of the soldering alloy in any one of the first to eleventh inventions.

A thirteenth invention is a preform solder.

The preform solder consists of the soldering alloy in any one of the first to the eleventh inventions.

A fourteenth invention is a soldering ball.

The soldering ball consists of the soldering alloy in any one of the first to eleventh inventions.

A fifteenth invention is a wire solder.

The wire solder consists of the soldering alloy in any one of the first to eleventh inventions.

A sixteenth invention is a resin flux cored solder.

The resin flux cored solder consists of the soldering alloy in any one of the first to eleventh inventions.

A seventeenth invention is a solder joint.

The solder joint includes the soldering alloy in any one of the first to eleventh inventions (the solder joint does not include a soldering alloy other than the soldering alloy in any one of the first to eleventh inventions).

An eighteenth invention is an electronic circuit board.

The electronic circuit board is joined by using the solder joint of the seventeenth invention.

A nineteenth invention further has the following features in the eighteenth invention.

The electronic circuit board further includes a high thermal resistance electronic part which has a higher thermal resistance temperature than the electronic part.

The high thermal resistance electronic part is joined to the electronic circuit board by using another solder joint.

The another solder joint includes another soldering alloy having a melting point higher than the liquidus temperature of the soldering alloy included in the solder joint.

A twentieth invention further has the following features in the eighteenth invention.

The electronic circuit board further includes a low thermal resistance electronic part which has a lower thermal resistance temperature than the electronic part.

The low thermal resistance electronic part is joined to the electronic circuit board by using another solder joint.

The another solder joint includes another soldering alloy having a melting point lower than the solidus temperature of the soldering alloy included in the solder joint.

A twenty-first invention is a multi-layer electronic circuit board.

The multi-layer electronic circuit board includes a first board and a second board.

The first board includes an electronic part joined by using the solder joint of the seventeenth invention.

The second board is laminated on the first board. The second board includes a high thermal resistance electronic part which has a higher thermal resistance temperature than the electronic part.

The high thermal resistance electronic part and the second board are joined by using another solder joint.

The another solder joint includes another soldering alloy having a melting point higher than the liquidus temperature of the soldering alloy included in the solder joint.

A twenty-second invention is a multi-layer electronic circuit board.

The multi-layer electronic circuit board includes a first board and a second board.

The first board includes an electronic part joined by using the solder joint of the seventeenth invention.

The second board is laminated on the first board. The second board includes a low thermal resistance electronic part which has a lower thermal resistance temperature than the electronic part.

The low thermal resistance electronic part and the second board are joined by using another solder joint.

The another solder joint includes another soldering alloy having a melting point lower than solidus temperature of soldering alloy included in the solder joint.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram showing a relationship between a content of In in Sn—In based alloy and a melting point thereof;

FIG. 2 is a diagram showing a relationship between a content of Ag in Sn-20In-Ag based alloy and the melting point thereof;

FIG. 3 is a diagram showing a relationship between a content of Bi in Sn-20In—Bi based alloy and the melting point thereof;

FIG. 4 is a schematic view showing a first example of an electronic circuit board;

FIG. 5 is a schematic view showing a second example of the electronic circuit board;

FIG. 6 is a schematic diagram showing a first example of a multi-layer electronic circuit board;

FIG. 7 is a schematic diagram showing a first example of a multi-layer electronic circuit board;

FIG. 8 is a diagram including cross-sectional SEM photographs of Example 2 and Referential example 2;

FIG. 9 is a diagram including cross-sectional SEM photographs of Example 3 and Referential example 4;

FIG. 10 is a diagram including cross-sectional SEM photographs of Example 2 and Referential example 2; and

FIG. 11 is a diagram including cross-sectional SEM photographs of Example 3 and Referential example 4.

DESCRIPTION of EMBODIMENTS

The present invention is described in detail below. In this specification, “%” of an element contained in a soldering alloy represents “mass %” unless otherwise specified. In addition, in this specification, the intermediate to low temperature range represents a temperature range from 160 to 210° C. An intermediate temperature range represents a temperature range above an upper limit of the intermediate to low temperature range (i.e., 210° C.). A low temperature range represents a temperature range below a lower limit of the intermediate to low temperature range (i.e., 160° C.). In addition, in this specification, a melting point represents a solidus temperature or a liquidus temperature.

1. Soldering Alloy

The soldering alloy according to the present invention includes an alloy composition consisting of 13-22% of In, 0.5-2.8% of Ag, 0.5-5.0% of Bi, 0.002-0.05% of Ni, and a balance Sn. Hereinafter, the elements constituting this alloy composition and their contents will be described.

1.1 In: 13-22%

In has a property of lowering the melting point of the soldering alloy. FIG. 1 is a graph showing a relationship between content of In in a Sn—In based alloy and the melting point thereof. As shown in FIG. 1, the melting point of the Sn—In based alloy tends to decrease as the content of In increases. However, when the content of In is more than 20%, the solidus temperature starts to decrease rapidly. When the content of In is greater than 25%, the solidus temperature drops to about 117° C. Therefore, the soldering alloy based on an alloy of which the content of In is more than 25% is not suitable as the soldering alloy for the soldering performed in the intermediate temperature range. In this respect, if an upper limit of the content of In is about 22%, the solidus temperature condition is satisfied. Therefore, this upper limit is 22%. From a viewpoint to satisfy the condition on the solidus temperature, a preferable upper limit is 21%, and a more preferable upper limit is 20%.

In the intermediate to low temperature range, the alloy of which the content of In is less than 5% forms a Sn-rich phase called a β-Sn phase. When the content of In is greater than 5%, the alloy forms a phase of InSn₄ compound called a γ phase. This γ phase is stably formed when the content of In is 5-25%. However, when the content of In decreases, there is a risk that a phase transformation occurs between the γ phase and the β-Sn phase in accompany with temperature change. When the phase transformation occurs, there is a risk that a mechanical reliability of the alloy will decrease because a deformation of the alloy will occur due to changes in volume. In this respect, when the lower limit of the content of In is 13%, this transformation can be suppressed. Therefore, this lower limit is 13%. From the viewpoint of the mechanical reliability, a preferable lower limit is 15%.

In addition, the γ phase has a brittle property as compared with SAC305. Therefore, if the content of In in the γ phase is increased, there is a risk that ductility of the soldering alloy may be lowered and the mechanical reliability of the soldering alloy may be lowered. Therefore, from the viewpoint to ensure the ductility, it is preferable that the upper limit of the content of In is not too large. A specific preferred upper limit is 17%.

1.2 Ag: 0.5-2.8%

Ag has a property of changing the melting point of the soldering alloy. FIG. 2 is a graph showing a relationship between the content of Ag in a Sn-20In-Ag based alloy and the melting point thereof. As shown in FIG. 2, the liquidus temperature is located in the intermediate to low temperature range. When the content of Ag is 2.8% or less, this liquidus temperature tends to decrease as the content increases. When the content of Ag is greater than 2.8%, the liquidus temperature will start to rise. Therefore, when the content of Ag is more than 2.8%, it may prevent the melting point from decreasing due to the addition of In. Therefore, the upper limit of the content of Ag is 2.8%. From the viewpoint to suppress the increase in the liquidus temperature, the preferable upper limit is 2.5%.

Ag and In form a Ag₂In compound. When the phase of this intermetallic compound is precipitated, the modification of the soldering alloy can be suppressed. From the viewpoint to exert this effect, the lower limit of the content of Ag is 0.5%. From the viewpoint to coarsen the precipitate and to enhance this effect, the preferable lower limit is 1.0%.

1.3 Bi: 0.5-5.0%

Bi has a property of lowering the melting point of the soldering alloy. FIG. 3 is a graph showing a relationship between content of Bi in a Sn-20In—Bi based alloy and the melting point thereof. As shown in FIG. 3, the liquidus temperature is located in the intermediate to low temperature range. This liquidus temperature tends to decrease as the content of Bi increases. However, it is not desirable that the melting point of the soldering alloy is too low due to the increase in the content of Bi. Therefore, the upper limit of the content of Bi is 5.0%. From the viewpoint to suppress the decrease in the liquidus temperature, the preferable upper limit is 2.5%.

Bi is dissolved in Sn in a certain amount. The solid solution of Bi makes it possible to suppress modification of soldering alloy. From the viewpoint to exert this effect, the lower limit of the content of Bi has been set to 0.5%. The preferable lower limit is 1.0% In addition, an excessive solid solution of Bi may reduce the ductility of the soldering alloy. From this viewpoint, it is preferable that the upper limit of the content of Bi is not too large. The specific preferred upper limit is 2.5%.

1.4 Ni

Ni has a property of fining an alloy organization. When the alloy organization is fined, the mechanical property of the soldering alloy is improved. From the viewpoint to exert this effect, the lower limit of the content of Ni has been set to 0.002%. The preferable lower limit is 0.003% and the more preferable lower limit is 0.004% On the other hand, an excessive miniaturization by Ni has a risk to lower the ductility of the soldering alloy. In addition, an excessive addition of Ni raise the liquidus temperature of the soldering alloy. From this viewpoint, it is desirable that the content of Ni is not too high. Therefore, the upper limit of the content of Ni is 0.05%. The preferable upper limit is 0.04% and the more preferable upper limit is 0.03%.

1.5 Sn: Balance

A balance of the soldering alloy of the present invention is composed of S n. Further, in addition to the essential elements described above, an unavoidable impurity may be contained in the soldering alloy Even if the unavoidable impurity is contained, it does not affect the effects due to the soldering alloy Examples of the unavoidable impurity include Pb and As.

1.6 Relationship in Content

In the soldering alloy according to the present invention, each content of In, Ag, Bi and Ni is as described above. However, from results of Examples described later, it is preferable that a relationship of these contents satisfies the following relationship (1).

0.9≤(In×Ni)×(Ag+Bi)≤3.4  (1)

In the relationship (1), In, Ni, Ag, and Bi represent each content of the respective elements (mass %).

The soldering alloy of which the content of In, Ag, Bi and Ni is within the above described range and also satisfies the relationship (1) is preferred from the viewpoint of the melting point and the mechanical property. From the viewpoint of an intended melting point and mechanical property, an upper limit value of the relationship (1) is more preferably 2.55.

2. Other Additive Elements

In addition to the essential elements described above, the following element may be optionally contained in the soldering alloy according to the present invention. In this instance, Sn constitutes the balance of the soldering alloy to which the optional element has been added.

2.1 at Least One Selected from P, Ge and Ga: 0.09% or Less

P, Ge or Ga have properties of suppressing an oxidation of Sn and improving a wettability of the soldering alloy. Therefore, these elements are optionally added to the soldering alloy according to the present invention. In particular, when the soldering alloy according to the present invention is used as a preform solder, at least one selected from these elements is preferably added because it is possible to suppress a discoloration of a surface of the soldering alloy.

When the at least one selected from these elements is added, the upper limit of the content is 0.09% in total. When the total content exceeds 0.09%, a fluidity of the soldering alloy on the solder surface may be inhibited. Each content of the respective elements is not particularly limited. However, a preferable content of P is 0.005-0.06% and a more preferable content is 0.005-0.01%. The preferable content of Ge is 0.003-0.06% and the more preferable content is 0.003-0.01%. The preferable content of Ga is 0.005-0.06% and the more preferable content is 0.005-0.01%.

2.2 Sb: 0.005-0.1%

Likewise Ni, Sb has a property of fining the alloy organization. Therefore, Sb is optionally added to the soldering alloy according to the present invention When Sb is added, its content is 0.005-0.1%. When the content of Sb is less than 0.005%, the miniaturization effect is not exerted. When the content of Sb is more than 0.1%, the liquidus temperature of the soldering alloy is increased.

3. Melting Point of the Soldering Alloy

The melting point of the soldering alloy according to the present invention is not particularly limited as long as it is within the intermediate to low temperature range. However, the solidus temperature of the soldering alloy according to the present invention is preferably 160° C. or more. When the solidus temperature is above 160° C., the following effect is expected in the step-soldering including the soldering performed in the intermediate to low temperature range. That is, it is possible to prevent the soldering alloy according to the present invention which has been subjected to the soldering and has been soldered from being re-melted during the soldering performed for a low temperature soldering alloy. Examples of the low temperature soldering alloy include Sn-58Bi and Sn-521n. The preferable solidus temperature is 165° C. or more.

Further, the liquidus temperature of the soldering alloy according to the present invention is preferably 210° C. or less. When the liquidus temperature is not exceed 210° C., the following effect is expected in the step-soldering including the soldering performed in the intermediate to low temperature range. That is, it is possible to prevent an intermediate or high temperature soldering alloy which has been soldered from being re-melted during the soldering performed for the soldering alloy according to the present invention. Examples of the medium temperature soldering alloy include SAC305. Examples of the high temperature soldering alloy include a soldering alloy of Sn-90Pb. The preferable liquidus temperature is 200° C. or less.

4. End-Usage of Soldering Alloy 4.1 Soldering Paste

The soldering alloy according to present invention is suitably used as a soldering paste. The soldering paste is produced by mixing a powdery soldering alloy with a flux containing a Rosin-based resin, an activator, a solvent, or the like. The flux is not particularly limited as long as it is commonly used in the art, and materials used therefor and blending ratio thereof are not particularly limited. The blending ratio (mass ratio) of the powdery soldering alloy and the flux is generally 90:10. However, this blending ratio is appropriately adjusted according to an end-usage of the soldering paste.

4.2 Preform Solder

The soldering alloy according to the present invention is also suitably used as a preform solder molded into a ribbon-shape, a disk-shape, a washer-shape, a tip-shape, or a ring-shape. The preform solder is produced by methods commonly known in the art. The shape of the preform solder is not limited to the above described shapes, and may be appropriately changed according to its end-usage. The preform solder may include the flux therein. The preform solder may be coated with the flux on its surface.

4.3 Soldering Ball

The soldering alloy according to the present invention is also suitably used as a soldering ball. The soldering ball is used to form a hemispherical bump in a semiconductor package such as ball-grid arrays (BGAs). The soldering ball is produced by methods commonly known in the art. When the soldering alloy according to the present invention is used as the soldering ball, its diameter is preferably in a range of 1-1000 μm. Further, a sphericity is preferably 0.90 or more, more preferably 0.95 or more, and most preferably 0.99 or more.

4.4 Wire Solder and Resin Flux Cored Solder

The soldering alloy according to the present invention is also suitably used as a wire solder processed into a wire. Further, the wire solder is also suitably used as a resin flux cored solder having the flux therein. The wire solder and resin flux cored solder are suitable for the soldering with a solder iron. The wire solder and resin flux cored solder are produced in a manner generally known in the art.

4.5 Solder Joint

The soldering alloy according to the present invention is also suitably used as a solder joint. The solder joint connects an electronic part such as an integrated circuit (IC) chip and a printed board (e.g., an interposer) in a semiconductor package. Alternatively, the solder joint joints to connect the semiconductor package and the printed circuit board. The solder joint is a connecting portion formed at a bonding portion. The solder joint is formed under common soldering conditions.

5. Electronic Circuit Board

When the soldering alloy according to the present invention functions as the solder joint, an electronic circuit board where an electronic part is joined via this solder joint corresponds to an electronic circuit board according to the present invention.

5.1 Single-Layer Electronic Circuit Board

FIG. 4 is a schematic diagram illustrating a first example of the electronic circuit board according to the present invention. A board 10 shown in FIG. 4 includes electronic parts 11 and 12. The board 10 is, for example, a printed-circuit board. The electronic parts 11 and 12 are, for example, IC chips. A maximum use temperature of the electronic part 11 is within the intermediate to low temperature range. The maximum use temperature of the electronic part 12 is above the lower limit of the intermediate temperature range (i.e., 210° C.). That is, a thermal resistance of the electronic part 12 is higher than that of the electronic part 11.

In the first example, the electronic part 11 is joined to the board 10 via a solder joint 13. The solder joint 13 is composed of the soldering alloy according to the present invention. On the other hand, the electronic part 12 is joined to the board 10 via a solder joint 14. The solder joint 14 is composed of the intermediate temperature soldering alloy or the high-temperature soldering alloy. That is, the solder joint 14 is composed of another soldering alloy having the melting point (more precisely, the solidus temperature) higher than the liquidus temperature of the soldering alloy according to the present invention.

FIG. 5 is a schematic diagram illustrating a second example of the electronic circuit board according to the present invention. Note that the electronic part 11 and the solder joint 13 shown in FIG. 5 are common to those shown in FIG. 4. Therefore, the descriptions for these elements are omitted. A board 20 shown in FIG. 5 includes an electronic part 21. The board 20 is, for example, a printed-circuit board. The electronic part 21 is, for example, an IC-chip. The maximum use temperature of the electronic part 21 is below the lower limit of the low temperature range (i.e., 160° C.). That is, the thermal resistance of the electronic part 21 is lower than that of the electronic part 11.

In the second example, the electronic part 21 is joined to the board 20 via a solder joint 22. The solder joint 22 is composed of a low temperature soldering alloy. That is, the solder joint 22 is composed of another soldering alloy having the melting point (more precisely, the liquidus temperature) lower than the solidus temperature of the soldering alloy according to the present invention.

5.2 Multi-Layer Electronic Circuit Board

FIG. 6 is a schematic diagram illustrating a first example of a multi-layer electronic circuit board according to the present invention. A board 30 shown in FIG. 6 is a multi-layer board in which aboard 32 and an interposer 33 are laminated on aboard 31. The board 31 is, for example, a printed-circuit board. The board 32 is, for example, a packaging board. The board 32 includes an interposer 33 and an electronic part 34. In the present invention, the board 32 and the interposer 33 corresponds to a first board or a second board. The interposer 33 includes an electronic part 35.

The electronic parts 34 and 35 are, for example, integrated circuit chips. The maximum use temperature of the electronic part 34 is above the lower limit of the intermediate temperature range. The maximum use temperature of the electronic part 35 is within the intermediate to low temperature range. That is, the thermal resistance of the electronic part 34 is higher than that of the electronic part 35.

In the first example, the electronic part 35 is joined to the interposer 33 via a solder joint 36. The solder joint 36 is composed of the soldering alloy according to the present invention. On the other hand, the electronic part 34 is joined to the board 32 via a solder joint 37. The solder joint 37 is also used for a junction between the boards 31 and 32 and the junction between the board 32 and the interposer 33. The solder joint 37 is composed of the intermediate and high soldering alloy. That is, the solder joint 37 is composed of another soldering alloy having the melting point (more precisely, the solidus temperature) higher than liquidus temperature of the soldering alloy according to the present invention.

FIG. 7 is a schematic diagram illustrating a second example of the multi-layer electronic circuit board according to the present invention. Note that the boards 31 and 32 and the interposer 33 shown in FIG. 7 are common to those shown in FIG. 6. Therefore, the descriptions for these elements are omitted. A board 40 shown in FIG. 7 includes an electronic part 41. The interposer 33 includes an electronic part 42.

The electronic parts 41 and 42 are, for example, integrated circuit chips. The maximum use temperature of the electronic part 41 is within the intermediate to low temperature range. The maximum use temperature of the electronic part 42 is below the lower limit of the low temperature range. That is, the thermal resistance of the electronic part 42 is lower than that of the electronic part 41.

In the second example, the electronic part 41 is joined to the board 32 via a solder joint 43. The solder joint 43 is composed of the soldering alloy according to the present invention. The solder joint 43 is also used for the junction between the boards 31 and 32 and the junction between the board 32 and the interposer 33. On the other hand, the electronic part 42 is joined to the interposer 33 via a solder joint 44. The solder joint 44 is composed of the low-temperature soldering alloy. That is, the solder joint 44 is composed of another soldering alloy having the melting point (more precisely, the solidus temperature) lower than the liquidus temperature of the soldering alloy according to the present invention.

6. Others

In the step soldering, the soldering by using a soldering alloy having a relatively higher melting point is performed earlier. The soldering by using a soldering alloy having a relatively lower melting point is performed later. The step soldering is performed using, for example, a reflow method. In the reflow soldering, it is preferable to raise an ambient temperature to a temperature about 5 to 20° C. higher than the liquidus temperature of the soldering alloy to be subjected to the soldering. Then, it is preferred to cool the ambient temperature at 2-3° C./sec. By performing such the reflow soldering, the miniaturization of the alloy organization is enhanced. Other bonding conditions are appropriately adjusted according to the soldering alloy and properties of bonding objects.

7. Examples

A soldering alloy consisting of alloy composition shown in Table 1 was prepared and the melting point of soldering alloy was measured. The reliability of these soldering alloy was evaluated by a shear test with cryogenic cycles.

7.1 Melting Point

Solidus temperature and liquidus temperature were carried out by the same DSC (Differential scanning calorimetry) method as JISZ 3198-1 measuring method. Samples of which the solidus temperature are above 160° C. were evaluated as “GD”, whereas those of which the solidus temperature are lower than 160° C. were evaluated as “PR”. Samples with solidus temperature above 165° C. were evaluated as “EC”. Samples with liquidus temperature below 210° C. were evaluated as “GD”. Samples higher than 210° C. were evaluated as “PR”. Samples with liquidus temperature below 200° C. were evaluated as “EC”.

7.2 Shear Test with Cryogenic Cycles

Solder alloy was atomized to give a solder powder. Solder powder was mixed with fluxes to produce a soldering paste. This soldering paste was printed on a 0.8-mm-thick printed board (material: FR-4) using a 100-μm-thick metal mask. The BGA component was mounted on the print board using a mounter. Then, reflow soldering was performed at a maximum temperature of 200° C. for a holding time of 60 seconds to obtain board samples.

Board samples were placed in a heat cycle tester set at low temperature −40° C., high temperature+100° C., and holding time of 10 minutes and removed at 1000 cycles. Thereafter, this test board was measured for shear strength (N) by a shear strength measuring device (STR-1000 manufactured by RHESCA Co., Ltd.) under a condition of 6 mm/sec. Samples having a shear strength of 30.00N or more were evaluated as “GD” by determining that they are at a level which can be used without problems in practical use. Samples with a shear strength of less than 30.00N were evaluated as “PR”. Samples for which the melting point was evaluated as “PR” were excluded from shear test.

The evaluation results are shown in Table 1 and Table 2.

TABLE 1 Sn In Ag Bi Ni Other elements (In*Ni)*(Ag + Bi) Solidus Liquidus Shear test Ex. 1 Balance 13 2.5 3 0.02 1.43 EC EC GD Ex. 2 Balance 15 2.5 2 0.02 1.35 EC EC GD Ex. 3 Balance 17 2.5 1.5 0.02 1.36 EC EC GD Ex. 4 Balance 20 1 1 0.05 2 GD EC GD Ex. 5 Balance 21 0.5 0.5 0.05 1.05 GD EC GD Ex. 6 Balance 17 0.5 1.5 0.02 0.68 EC EC GD Ex. 7 Balance 17 1 1.5 0.02 0.85 EC EC GD Ex. 8 Balance 17 2 1.5 0.02 1.19 EC EC GD Ex. 9 Balance 17 2.8 1.5 0.02 1.462 EC EC GD Ex. 10 Balance 18 1.5 0.5 0.04 1.44 EC EC GD Ex. 11 Balance 17 2.5 2 0.02 1.53 EC EC GD Ex. 12 Balance 14 1 5 0.03 2.52 EC EC GD Ex. 13 Balance 17 2.5 1.5 0.002 0.136 EC EC GD Ex. 14 Balance 17 2.5 1.5 0.005 0.34 EC EC GD Ex. 15 Balance 17 2.5 1.5 0.05 3.4 EC EC GD Ex. 16 Balance 17 2.5 1.5 0.02 P: 0.005 1.36 EC EC GD Ex. 17 Balance 17 2.5 1.5 0.02 Ge: 0.003 1.36 EC EC GD Ex. 18 Balance 17 2.5 1.5 0.02 Ga: 0.005 1.36 EC EC GD Ex. 19 Balance 17 2.5 1.5 0.02 P: 0.01 1.36 EC EC GD Ex. 20 Balance 17 2.5 1.5 0.02 Ge: 0.01 1.36 EC EC GD Ex. 21 Balance 17 2.5 1.5 0.02 Ga: 0.01 1.36 EC EC GD Ex. 22 Balance 17 2.5 1.5 0.02 P: 0.005 1.36 EC EC GD Ge: 0.005 Ex. 23 Balance 17 2.5 1.5 0.02 Sb: 0.005 1.36 EC EC GD Ex. 24 Balance 17 2.5 1.5 0.02 Sb: 0.1 1.36 EC EC GD Ex. 25 Balance 15 2.5 1 5 0.015 0.9 EC EC GD Ex. 26 Balance 17 2.5 1.5 0.02 P: 0.03 1.36 EC EC GD Ex. 27 Balance 17 2.5 1.5 0.02 Ge: 0.03 1.36 EC EC GD Ex. 28 Balance 17 2.5 1.5 0.02 Ga: 0.03 1.36 EC EC GD Ex. 29 Balance 17 2.5 1.5 0.02 P: 0.06 1.36 EC EC GD Ex. 30 Balance 17 2.5 1.5 0.02 Ge: 0.06 1.36 EC EC GD Ex. 31 Balance 17 2.5 1.5 0.02 Ga: 0.06 1.36 EC EC GD Ex. 32 Balance 17 2.5 1.5 0.02 P: 0.09 1.36 EC EC GD Ex. 33 Balance 17 2.5 1.5 0.02 Ge: 0.09 1.36 EC EC GD Ex. 34 Balance 17 2.5 1.5 0.02 Ga: 0.09 1.36 EC EC GD Ex. 35 Balance 17 2.5 1.5 0.02 P: 0.04 1.36 EC EC GD Ge: 0.05 Ex. 36 Balance 17 2.5 1.5 0.02 Ge: 0.02 1.36 EC EC GD Ga: 0.03 Ex. 37 Balance 17 2.5 1.5 0.02 P: 0.01 1.36 EC EC GD Ga: 0.01

TABLE 2 Other Sn In Ag Bi Ni elements (In*Ni)*(Ag + Bi) Solidus Liquidus Shear Test Ref. 1 Balance 20 2.8 — PR EC — Ref. 2 Balance 15 2.5 2 — EC EC PR Ref. 3 Balance 16 2.5 2 — EC EC PR Ref. 4 Balance 17 2.5 1.5 — EC EC PR Ref. 5 Balance 8 2 1.5 0.01 0.28 GD PR — Ref. 6 Balance 25 2 1.5 0.01 0.875 PR GD — Ref. 7 Balance 15 2 1.5 0.3 15.75 GD PR — Ref. 8 Balance 8 3.5 0.5 0.5 16 GD PR — Ref. 9 Balance 12 3.5 0.5 1.5 72 GD PR — Ref. 10 Balance 12 2 2 1 46 GD PR — Ref. 11 Balance 12 2.8 2 1 57.6 GD PR — Ref. 12 Balance 12 2 1 2 72 GD PR — Ref. 13 Balance 12 2.8 1 2 91.2 GD PR — Ref. 14 Balance 18 2 2 1 72 GD PR — Ref. 15 Balance 18 2.8 2 1 86.4 GD PR — Ref. 16 Balance 18 2 1 2 108 GD PR — Ref. 17 Balance 18 2.8 1 2 136.8 GD PR —

From the results in the melting point of Examples 1-37, it was found that each of these examples satisfied the condition with respect to the melting point. Example 1 had the solidus temperature of 180° C. and the liquidus temperature of 196° C. Example 2 had the solidus temperature of 173° C. and the liquidus temperature of 195° C. Example 3 had the solidus temperature of 167° C. and the liquidus temperature of 191° C. These results prove that the intended melting point was realized by adding an appropriate amount of In, Ag and Bi having the property of lowering the melting point of Sn as a main component. From the shear test results, it was also found that these examples were excellent in the cold-heat cycling resistance. These results prove that the intended mechanical property was realized by adding an appropriate amount of Ag, Bi and Ni that improves the mechanical property.

The result in the melting point of Referential example 1 showed that the solidus temperature of Referential example 1 was 154° C., being lower than 160° C. This result indicates that the solidus temperature continues to decrease as the content of Ag increases.

The results in the melting point and the shear strength of Referential examples 2-4 indicate that these referential examples are inferior in the cold-cycle resistance, although their melting points are well evaluated. The results in the shear strength indicate that absence of Ni may have an effect.

The results in the melting point of Referential examples 5, 8-13 indicate that these referential examples had the liquidus temperature above 210° C. These results indicate that the liquidus temperature is not sufficiently lowered when In was added in a small amount. The results in the melting point of Referential example 8-13 indicate that the liquidus temperature may be increased when In was adding in a large amount. This possibility is supported by the fact that the results in the liquidus temperature of Referential examples 7, 14-17 and those of Referential examples 8-13 were the same.

The result in the melting point of Referential example 6 showed that the solidus temperature of Referential example 6 was 135° C. and it was found that the solidus temperature was lower than 160° C. This result indicates that the solidus temperature drops sharply when the added amount of In is higher than 25%.

7.3 Observation of Alloy Organization

To confirm the discussion in Referential examples 2-4, the soldering alloy of Examples 2 and 3 and the soldering alloys of Referential examples 2 and 4 were prepared. The soldering alloy of Referential example 2 has a composition obtained by removing Ni from that of Example 2. The soldering alloy of Referential example 4 has a composition obtained by removing Ni from that of Example 3.

A resin mold was used to form these soldering alloys to obtain samples. Each of the samples was polished by about half, and the polished portion was photographed with a FE-SEM at a magnification of 1000 times. FIG. 8 is a cross-sectional SEM photography of Example 2 and Referential example 2. FIG. 9 is a cross-sectional SEM photography of Example 3 and Referential example 4. It was found from FIGS. 8 and 9 that the alloy organization of Example 2 or 3 in which Ni is included was fined as compared to that of the corresponding referential examples. This results indicate that the considerations discussed in Referential examples 2-4 may be reasonable. Note that the black portions shown in FIGS. 8 and 9 represent intermetallic compounds lost by the polishing.

In addition, the solder powders prepared from these soldering alloys was used to obtain board samples. The method for preparing the board samples was performed according to that in the shear test. Then, a bonding interface of the BGA terminal and the printed board was photographed with the FE-SEM at a magnification of 1000 times. FIG. 10 is a cross-sectional SEM photography of Example 2 and Referential example 2. FIG. 11 is a cross-sectional SEM photography of Example 3 and Referential example 4. It was found from FIGS. 11 and 12 that the miniaturization of the alloy organization in Example 2 or 3 were maintained even in a state of the BGA terminal. The results indicate that soldering alloy according to present invention may be useful as the BGA terminal and the solder joint.

REFERENCE SIGNS LIST

-   -   10, 20, 30, 31, 40 Board     -   11, 12, 21, 34, 35, 41, 42 Electronic part     -   13, 14, 22, 36, 37, 43, 44 Solder joint     -   33 Interposer 

1. A soldering alloy comprising an alloy composition consisting of 13-22 mass % of In, 0.5-2.8 mass % of Ag, 0.5-5.0 mass % of Bi, 0.002-0.05 mass % of Ni, and a balance Sn.
 2. The soldering alloy according to claim 1, wherein the alloy composition further contains at least one selected from P, Ge and Ga in total of 0.09 mass % or less.
 3. The soldering alloy according to claim 1, wherein the alloy composition further contains 0.005-0.1 mass % of Sb.
 4. The soldering alloy according to claim 1, wherein the content of In is 15-20%.
 5. The soldering alloy according to claim 4, wherein an upper limit of the content of In is 17%.
 6. The soldering alloy according to claim 1, wherein the content of Ag is 1.0-2.5%.
 7. The soldering alloy according to claim 1, wherein the content of Bi is 1.0-2.5%.
 8. The soldering alloy according to claim 1, wherein the content of Ni is 0.003-0.04%.
 9. The soldering alloy according too claim 1, wherein the content of In, Ag, Bi, and Ni satisfies the following equation (1), 0.9≤(In×Ni)×(Ag+Bi)≤3.4  (1) wherein, in the relationship (1), In, Ni, Ag, and Bi represent each content of the respective elements.
 10. The soldering alloy according to claim 1, wherein a solidus temperature is 160° C. or more and a liquidus temperature is 210° C. or less.
 11. The soldering alloy according to claim 10, wherein the solidus temperature is 165° C. or higher and the liquidus temperature is 200° C. or lower.
 12. A soldering paste consisting of the soldering alloy according to claim
 1. 13. A preform solder consisting of the soldering alloy according to claim
 1. 14. A soldering ball consisting of the soldering alloy according to claim
 1. 15. A wire solder consisting of the soldering alloy according to claim
 1. 16. A resin flux cored solder consisting of the soldering alloy according to claim
 1. 17. A solder joint consisting of a soldering alloy comprising an alloy composition consisting of 13-22 mass % of In, 0.5-2.8 mass % of Ag, 0.5-5.0 mass % of Bi, 0.002-0.05 mass % of Ni, and a balance Sn, wherein the solder joint does not include another soldering alloy other than the soldering alloy comprising the alloy composition.
 18. An electronic circuit board comprising an electronic part joined by using the solder joint according to claim
 17. 19. The electronic circuit board according to claim 18, further comprising a high thermal resistance electronic part which has a higher thermal resistance temperature than the electronic part, wherein the high thermal resistance electronic part is joined by using another alloy having a melting point higher than the liquidus temperature of the soldering alloy included in the solder joint.
 20. The electronic circuit board according to claim 18, further comprising a low thermal resistance electronic part which has a lower heat resistance temperature than the electronic part, wherein the low thermal resistance electronic part is joined by using another solder joint including another soldering alloy having a melting point lower than the solidus temperature of the soldering alloy.
 21. A multi-layer electronic circuit board, comprising: a first board including an electronic part joined by using a solder joint consisting of a soldering alloy comprising an alloy composition consisting of 13-22 mass % of In, 0.5-2.8 mass % of Ag, 0.5-5.0 mass % of Bi, 0.002-0.05 mass % of Ni, and a balance Sn, wherein the solder joint does not include another soldering alloy other than the soldering alloy; and a second board including a high thermal resistance electronic part which is laminated on the first board and has a higher thermal resistance temperature than the electronic part, wherein the high thermal resistance electronic part and the second board are joined by using another solder joint including another soldering alloy having a melting point higher than the liquidus temperature of the soldering alloy included in the solder joint.
 22. A multi-layer electronic circuit board, comprising: a first board including an electronic part joined by using the solder joint according to claim 17; and a second board including a low thermal resistance electronic part which is laminated on the first board and has a lower thermal resistance temperature than the electronic part, wherein the low thermal resistance electronic part and the second board are joined by using another solder joint including another soldering alloy having a melting point lower than the solidus temperature of the soldering alloy included in the solder joint. 